Preparation of water-soluble phthalocyanine sulfonamide dyestuffs



United States Patent 3,185,701 PREPARATION OF WATER-SOLUBLE PHTHALO- CYANINE SULFONAMIDE DYESTUFFS Marco Tessandori, Milan, and Aldo Pasquarelli, Seveso, Milan, Italy, assignors to Aziende Colori Nazionali Aflini ACNA S.p.A., Milan, Italy No Drawing. Filed Feb. 25, 1963, Ser. No. 260,828 Claims priority, applicgatioigzltaly, Feb. 27, 1962,

1 Claim. c1. 260-4145 The present invention relates to water-soluble phthalocyanine dyestulfs which are particularly suitable for direct dyeing on vegetable fibers, particularly cotton. The present invention also relates to a method of preparing such dyestuffs.

Products obtained by reacting phthalocyanine-sulfonylchlorides with amines are known. More particularly,

German Patent 696,591, describes the reaction between phthalocyanine-tetrasulfonylchlorides and cyclohexylamine; the sulfonamides thus obtained, wherein all the SO Cl groups are transformed into SO' NHC H are all insoluble in water.

Phthalocyanine compounds exhibiting a degree of solubility in water are also known. These have been obtained -by reacting directly a phthalocyanine-sulfonylchloride with an aliphatic or aromatic amine so that a substitution of only a part of the SO Cl groups present takes place, and the other groups are then hydrolyzed to sulfonic groups by boiling, for instance, with water.

We have now surprisingly found that a ph-tha locyaninetr-i-sulfonamide or a phthal-ocyanine-tetra-sulfonamide can be made to undergo a partial hydrolysis by treatment with concentrated H 80 phth alocyanine dyestuffs can be obtained whose properties'do not depend in large extent on the conditions of the hydrolysis. The analysis allows to calculate for these dyestuifs a general formula of the type (1) HSOa SO2NHR x SOzNHR wherein Ph is the residue of copper phthalocyanine of the type Xis'either --SO H or H, and R is a hydrogen radical selected from the group consisting of cyclohexyl, phenyl and tolyl.

The present invention also provides a process for the preparation of the above-mentioned water soluble phthalocyanine dyestuffs.

This process comprises treating a compound of the formula:

RNHSOQ SOZNHR Y sozNHR (2) wherein Y is H or the radical S0 NHR and wherein Ph and R have the previously mentioned meanings with concentrated H at a temperature of about 30 C., l

' tolyl.

3,185,701 Patented May 25, 19 65 Ice followed by pouring into water, salting and filtration, to.

thereby etfect' a partial hydrolysis. v The advantage of this method for the preparing of water soluble phthalocyanine dyestuffs resides in the fact that one can regu- 1 late the degree of hydrolysis, in that the finished dyestutf retains a definite number-of sulfamido groups. This fact insures a greater uniformity of properties.

The two sulfamido groups also result in a higher water solubility-of the product also if the experimental conditions are widely changed: for instance the temperature may vary from 25 to 65 0., the time of hydrolysis from 2 to 20 hours, the concentration of sulphuric acid from 94 to percent.

The compounds of the Formula 2 may be prepared according to the known art. Such compounds can, for

instance, be obtained by reacting one mole of copper phthalocyanine with 3 moles (when Y is H) or with 4 moles (when Y is SOgNHR) of chlorosulfonic acid and treating the product thus obtained with 3 or 4 moles of an amine RNH wherein R is cyclohexyl, phenyl or It is preferable to complete the sulfochlorination reaction with addition of P01 or thionyl chloride.

The water soluble phthalocyanine dyestuffs comprised in theFormula 1, .and particularly, the dyestuff having the formula:

V CH -CH SO NH-CH CH,

clan-0Q,

/CH3 CHE-CH3 have characteristics of improved affinity, purity and fastness as compared to the previously known ph-thalocyanine dyestuffs.

The following examples will further illustrate the invention. All parts are by weight unless otherwise indicated.

7 Example 1 4 g. phthalocyanine-tetra-sulfocyclohexylamide which may be represented by the formula:

GH -CH Ph (SO NHF-C CH CH -O 4 SOgNH-CH SOzNH-C turquoise shade which is very intense, pure, and which is resistant to wetness and to creasing.

Example .2

4 g. copper phthalocyanine are dissolved into 72 g.

i sulfuryl hydrochloride, SO HCl, and the whole is heated at 140 C. for 4 hours.

The reaction is completed by addition of 8 g. PCl at 80 C. The mixture is cooled,

' poured into cold water, and filtered in the cold. The

mass is treated again with Water at 2-3 C. in the presence of 12 g. Na CO and successively 36 g. cyclohexylamine are added.

The whole is agitated at 20 C. until the condensation is complete.

The phthalocyanine-tetra-sulfocyclohexylarnine thus obtained, after drying, is treated as described in Example 1. Equivalent results are obtained.

Example 3 In the preparation of the sulfochloride, thionyl chloride is used instead of PCl Otherwise the procedure is as described in Example 2. The results obtained are equivalent.

Example 4 presence of 3 g. sodium carbonate and then 5.5 g. cyclohexylamine are added.

Then the Whole is agitated at 20 C. until the condensation is complete.

The product so obtained, after drying is treated with sulphuric acid as described in Example 1.

A dyestuff isobtained which dyes the cotton with a blue, intense, fast shade.

The elementary analysis allows to calculate the following formula? GH -CH,

SO NH-CH /0H,

OH -CH;

CH;OH H

sown-0H /CH2 QH2-OH HSOg-Ph Variations can,'of course, be made without departing from the spirit of the invent-ion.

Having thus described the invention What it is desired to secure and claim by Letters Patent is:

A process for the preparation of a phthalocyanine dyestuff of the formula;

X SO NHR (1) said process comprising partially hydrolyzing a com pound of the formula:

RNHSO:

wherein Ph is the residue from copper phthalocyanine, R is selected from the group consisting ofcyclohexyl, phenyl and tolyl, and Y is selected from the group consisting of SO NHR and H, by treating said compound with concentrated H at a temperature of about 30 C., treating the resultant compound, which contains two -SO NHR groups, with Water and thenprecipitating by salting. 1

SO NHR S OzNHR References Cited by the Examiner UNITED STATES PATENTS 2,285,359 6/42 Rosch et al. 260314.5 2,300,572 11/42 Hoyer et a1. 260--314.5 2,759,950 4/56 Tartter 260314.5 3,042,475 7/62 Heslop et al. 260314.5

, v FOREIGN PATENTS 520,199 4/40 Great Britain.

. OTHER REFERENCES Groggins: Unit Processes in Org. Synthesis, McGraw- 46 Hill Co., New York (1947), pages672 and 673.

IRVING MARCUS, Primary Examiner.

NICHOLAS S. RIZZO, WALTER A. MODANCE,

' i Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 18S 701 May 25 1965 Marco Tessandori et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1 line 58, for "Xis" read X is same line 58, for "hydrogen radical" read hydrocarbon radical Signed and sealed this 26th day of October 1965.

(SEAL) Allest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

